Pest control



ov. so, res

Pateted 2,335,384 7 rest cen'racrl Euclid W. Bonsqnet, .i'ames E'Kirby,and Norman E. Sear-1e, Wgton, Del, as'signors to E. I. du Pont deNemours 8; Company, Wilmington, DeL, a. corporation of Delaware NoDrawing. Application April 24, 1940, Serial No. 331,390

22 Claims.

This invention relates to pest control and is particularly directed tocompositions suitable for controlling various economically harmfulorganisms which commonly infest and attack plant and animal mattereither in its natbe obtained by the condensation of a ketaldone and anitro compound containing a nitro methyl group NO2CH2. The termketaldone refers generically to aldehydes and ketones. The reaction bytype may be represented by A nitroethylene then has the type formulaR1R2C=C(R3) N02 4502 (1904); by Kobayashi in $01. Papers Inst.

Phys. Chem. Research (Tokio) 6, 149-65 (1927); by Meisenheimer and(Io-workers in Ann. 68,

202-58 (1929), and various adaptations of these processes to particularnitroethylenes. The nitroethylenes may also be prepared by othermethods. For example, m-, or p-nitrocinnamic acid on treatment withstrong nitric acid loses carbon dioxide and yields the corresponding1-nitro- 2(nitrophenyl) ethylene; direct nitration of styrene givesbeta-nitrostyrene; and

dehydro-acetylation of l-acetoxy-Z-nitropropane yields 2-nitropropene.Thus nitroethylenes may be prepared in widely difiering manners, andhowever prepared are compounds of the type formula R1R2C=C(R3) N02.

Now it has been found that the class of compounds described asnitroethylenes are toxic to a surprisingly wide variety of organisms,such as bacteria, fungi and insects, and other economically andphysiologically harmful lower forms of life. Compounds containing thenitroethylene are efl'ective in controlling one or ore types of pests,though toxicity and specifl igy varyconsiderably according to the natureof the substituent groups. Nonetheless, all available data indicate thatthe nitroethylene group is inimical to living plant and animal organismsin many forms.

Evaluationoia wide variety of nitorethylenes synthesized from the mosteasily and ec0nom ically available raw materials in which the radicalsR1R2 and R3 of the type formula are widely diiferent indicates clearlythat toxicity attaches to the nitroethylene group and thatsubstituentgroups merely increase or, possibly, particularly in connection withcertain pests, decrease the toxic effect of the compound. Significantbut not exhaustive data to this eifect follow;

The high efiiciency of the nitroethylenes in controlling the growth ofdifferent types of fungi is shown by the data of the following table.The

results are those obtained by making a dispersion of the fungicide insterile liquid malt agar (pH of 5.7) followed, after hardening, byinoculation with a suspension of the appropriate fungus organisms.

TABLE I Concentration efi'ective against- Compound Mixed PenicilliumAsperqillua lumber 'm'ger molds 2-nitro-l-phenylpropene 1:32, 000 1:32,000 i-chloro-beta-nitrostyrena 1:32, 000 1:16, 0002-nitro-1-phenylbutene 1:16, 000 1:16, 000 2-nltro-1-phenylpentene 1:16,000 1:16, 000 2-carboxy-beta-nitrostyrene 1:1, 000 1:1, 000i-(alphe-iuryl)-2-nitro-etl1ylene 1:60. 000 1:60. 000 2-metoxy-beta-nitrostyrene.-. 1:32, 000 1:32, 0004-isoprogyl-beta-nitrostyrena 1:32, 000 1 :16, 000 Salicyli enenltromethnne 1:4. 000 1 :4, 000 2 chloro-fl-beta-dinltrostyren 1:4. 000 1:4, 0002-chloro beta-nitrostyrene. 1:32, 000 1:16, 0001-nitro-2-m-tolylethylene 1:32, 000 1 :32. 0003,4dimethoxy-beta-nitr0styrene. 1:8, 000 1:4, 000 2-nltropro ene 1:2,000 1:2, 000 3,4-methy enedioxy-betamitrostyrena 1:4, 000 1:4, 0004-methoxybeta-nltrostyrene 1:16, 000 1:16, 000 3-beta-dinitrostyrene. 11:4, 000 1:8, 000 4-phenyl-1-nitro-1,3-butadiene. 1:16, 000 1:16. 0001(p-chlorophenyl) 2-nitropro ene 1:4, 000 1:4, 000B-ethyoxyi-hydroxy-betatrostyrene.-. 1:250 1:2502,4-dimethoxy-beta-nitrostyrene 1:2, 000 1:250 4-11(ROXY-31116thOXY-bGtB-Illtl'OStYl'Bll 1:4, 000 1:2, 000 l-ntro-3-phenylpropene 1:1, 000 1:1, 000 Beta-nitrostyrene 1:60, 000 1:60,000

trostyrene and 1-(alpha-furyl-2-nitroethylene were effective at theexceptionally high dilution of 1:60,000. The precise" limit was notdetermined since the next highest dilution was 1: 120,000 so that itmight be more proper to say that these compounds were effectivesomewhere between 1 and 2 parts per 120,000 parts. the same conditionsalpha-nitronapthalene is effective against the mixed lumber molds at1:2000 to 1:4000. Para-nitrophenol similarly is effective at 1:4000 to1:8000.

The agents of this invention are also efiective as bactericides, thoughonly moderately so. Toble II is illustrative and shows concentrationrequired to inhibit growth of the organism.

These compounds were tested in 2.3% Bacto Nutrient Agar which had a pHof about 6.8.

The nitroethylenes are also effective in the control of insect pests.The data of Table III demonstrates the relative activity of eighteennitroethylenes in killing clothes moth larvae and for protectingtextiles from their depredations.

TABLE III Tineola Area of Compound gggg fabric kmed damaged Per cent Percent i-(dimethylamlno) -bete-nitrostyrene 19 382-chloro-o-beta-dlnitrostyrene 63 10 2-chloro-beta-nitrostyrcne r 1001-nitro-2-m-tolylethylene 100 0 3,4-d1methoxy-b eta-nitrostyrena 68 5l-(p;chloropher 1yl)-2-nitropropene. 100 8 Sodium beta-nitrostyreneo-sulfonate 93 3 3-beta-d1nitrostyrene 80 94-lsopropyl-beta-nitro5tyrene. 100 l 2-mcthoxy-b et a-nitrostyrene 95 43-cthoxy-4-hydroxy-beta-nitrostyren 85 302,4-dimcthoxy-beta-nltrostyrene 40 254-hydroxy-3-methoxy-beta-nitrostyrene. 80 18 1-n1tro-3-phenylpropenc r20 50 3,4-methylenedloxy-beta-nitrostyrene 55 15 4-m cthoxy-beta-nitrostyrene 95 26 Sollcyl denenitromethane 100 35Beta-nitrostyrene 40 15 The above results are those obtained underrigorous test conditions. For each test vigorous moth larvae areconfined with approximately two square inches of fiuffy woolen testfabric which had been impregnated with about 2% solution of the testcompound and dried. The data are recorded after a two-weeks interval.The damage is evaluated by estimating the per cent of surface the nap ofwhich has been fed upon.

The nitroethylenes may be used to prevent decay and putrefaction ofmaterials such as rawhides, glues, gelatins, carbohydrate pastes,glyptal resins, ropes, lumber, fabrics, leather and other natural orfabricated animal or plant matter subject to attack and decomposition bymicroorganisms. They may also be used to control fungous diseases inliving plant matter, especially for disinfecting seeds and dormantplants. They may also be used for the control of depredatory insects andlike animal organisms Under The highly volatile nitroethylenes may beused in fumigation, and most of them are su-fliciently volatile to havesome fumigating action. The following table shows the fumigant activityof Z nitroprOpene in connection with 'the clothes moth larvae, thecarpet beetle larvae and the confused flour beetle, adult and larvae.

TABLE IV Efiect of Z-nitropropene vapor on insects Kill at concentrationexpressed as 00. of liquid Insect Compound per 3.0 cc. 1.5 cc. 0.75 cc.

Per cent Per cent Per cent Tineola biaelliella {2-nitropropene 100 100larvae. Carbon tetrachloride. 100 100 0 Atiagenus piceus 2-nitropropeno70 70 20 larvae. Carbon tetrachlonda 70 56 0 Confused flourz-nltropropene 100 100 100 beetle adults. Carbon tetrachloride 100 100 0Confused flour 2-nltropropene 100 100 100 larvae. Carbon tetrachlorida83 100 0 The nitroethylenes containing less than six carbon atoms aremost suitable as fumigants.

Application of nitroethylenes for the various purposes disclosed may bemade from solutions in suitable solvents, such as alcohol, benzene, andpetroleum naphtha, or from dispersions in aqueous or other media, or inthe form of a dust. They may be used in combination-With supplementaryagents, such as talc, bentonite, tricalcium phosphate, various clays,spreading agents, stickers and other adjuvants commonly used in pestcontrol compositions; They may also be used in combination with otherpest control agents, such as copper and sulfur fungicides or organicfungicides, lead arsenate, phenothiazine, barium fluosilicate, xanthone,pyrethrum, rotenone, thiocyanates, methyl bromide and various otheragents commonly used in fungicidal and insecticidal applications. Theproducts of this invention should not be used with alkali or alkalineagents, and preferably are compounded in and used in media having a pHof less than 7.0. Caution should be used in using these products sincemany of them are lachrymatory and irri tant to the skin.

While we have illustrated our invention with reference to certainspecific nitroethylenes, it is to be understood that in its broaderaspects We do not desire to be limited to any particular nitroethylene.Thus, our invention includes compounds of the type R1R2C=C(R3) NO: inwhich R1 and R2 are the radicals of a ketaldone and R3 is eitherhydrogernalkyl, aralkyl or aryl. The alkyl, aralkyl and aryl groups maybe substituted or unsubstituted and without qualification are meant toinclude both.

Certain of the nitroethylenes of this invention may be classed ascompletely aliphatic, in

assasss which case the radicals R1 and R2 are the radicals of acompletely aliphatic ketaldone and R3 is hydrogen or alkyl. The alkylgroup may be cyclic or acyclic and is intended to include both unlessotherwise qualified. Compounds of this class include l-nitropropene,2-nitropropene, 3-

essential active ingredient an aryl nitroethylene. and a carriertherefor.

5. A pest 'control'composition containing as an essential activeingredient a compound of the type R1R2C=C(Ra)NO2 in which R1 and R: arethe radicals of an aromatic. ketaldone and R3 is selected from the groupconsisting of hydrogerl, alkyl, aralkyl and aryl, and a carriertherefor.

6. In the art of pest control the method of immunizing organic matterfrom attack by economically harmful organisms which comprises treatingsaid material with a compound of. the

and alkyl groups.

densation of a nitro-paraflin with an aralkyl.-

ketaldone. Compounds such as 4-phenyl-2-nitro-2-butene, 4-nitro-6-phenyl- 4-hexene, and 2- methyl-4-phenyl-1-nitrobutene; which arereadily available from ketaldones such as beta-phenylacetaldehyde,cinnamic aldehyde, and beta-phenylethyl methyl ketone and variousaliphatic a1 pha-nitro compounds are typical.v

Another distinct group includes compounds in which at least one of theradicals R1, R2 and Rs is aromatic. These may be obtained by thecondensation of a suitable aromatic ketaldone such as acetophenone,benzophenone,piperonal, furfural, vanillin, anisaldehyde, benzaldehyde,salicylaldehyde andthe like, with a suitable nitro compound, or bycondensing any suitable ketaldone with omega-nitrotoluene and similarnitromethylbenzenes. Beta-nitrostyrene and 1- (alpha-furyl)-2-nitroethylene are typical of those in the group consisting ofhydrogen, alkyl, aralkyl which R1 and R: are radicals of an aromaticaldehyde and 1-nitro-2,2-diphenylethylene and rophenyDnitroethylene, andl-naphthyl-l-nitro- 2,2-diphenylethylene.

We claim: a o 1. A pest control composition containing as an essentialactive ingredient a compound containing the nitroethylene structure 2.In the art of pest control the method of immunizing organic matter fromattack by economically harmful organisms which comprises treating saidmaterials with a compound containing the nitroethylene structure 3. Apest control composition containing as an essential active ingredient acompound of the type R1RzC =C(Ra)NOz in which R1 and R2 are the radicalsof a ketaldone and R3 is selected from the group consisting of hydrogen,alkyl, aralkyl and aryl radicals, and a carrier therefor.

4. A pest control composition containing as an type R1R2C=C(R3) N02 inwhich R1 and R2 are the radicals of an aromatic aldehyde and R3 isselected from the group consisting, of hydrogen 7. A pest controlcomposition containing as an -essential active ingredient a beta-nitroarylethylene, and a carrier therefor.

8.'A pest control composition containing as an essential activeingredient a compound of the type R1R2(:C(Ra) N02 in which R1 and Re arethe radicals of an aliphatic ketaldone and Rais selected from the class.consisting of hydrogen and alkyl radicals, and a carrier therefor.

9. A fungicidal composition containing asan essential active ingredienta compound of the type R1RzC=C(R3) NOa in which R1 and Rs are theradicals of a ketaldone andRa is selected from and aryl radicals and acarrier therefor.

10. A fungicidal composition containing as an essential activeingredient a compond of the type R1R2C=C(Ra)NOa in which R1 and Re arethe radicals of an aromatic ketaldone and R: is selected from the groupconsisting of hydrogen, alkyl, aralyl and aryl and a carrier therefor.

11. A fungicidal composition containing .as an essential activeingredient a compound of the type R1R2(?-C(Ra)N0z in which R1 and Rs arethe radicals of an aliphatic ketaldone and Rs is selected from the classconsisting of hydrogen and alkyl radicals, and a carrier therefor.

12. A fungicidal composition containing as an essential activeingredient an aryl nitroethylene, and a carrier therefor.

13. A fungicidal composition containing as an essential activeingredient a beta-nitroarylet hylene, and a carrier therefor.

14. In the art of pest control the method of immunizing organic matterfrom attack by'economically harmful microorganisms which comprisestreating said material with a compound of the type R1R2C=c(R3) NO: inwhich R1 and R2 are the radicals of an aromatic aldehyde and Re isselected from the group consisting of hydrogen and alkyl groups.

15. In the art of pest control the method of destroying pestiferousorganisms in infested organic material which comprises exposing theinfested material in a closed space to the vapors of an alkylnitroethylene containing less than six carbon atoms.

16. A pest control composition containing as an essential activeingredient 1- (alpha-furyl) -2- nitroethylene, and a carrier therefor.

17. A pest control composition containing as an essential activeingredient 2-nitropropene, and a carrier therefor.

18. A fungicidal composition containing as an essential activeingredient beta-nitrostyrene, and a carrier therefor. I

19. A fungicidal composition containing as an essential activeingredient l-(alpha-furyl) -2- nitroethylene, and a carrier therefor.

20. A pest control composition containing as an essential activeingredient a compound of the type R1R2C=C(R3)NO2 in which R1 and R2 arethe radicals of a ketaldone and R3 is a radical selected from the groupconsisting of hydrogen i and aliphatic and aromatic radicals, and acarrier therefor.

21. In the art of pest control the method of destroying pestiferousorganisms in infested material which comprises incorporating in the in-Patent N05 2,555,58Lfl CERTIFICATE OF CORRECTION..

EUCLID W, BOUSQUET, ET AL.

fested material a compound containing the nitroethyiene structureNovember 30,, 1915 'It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionas foilows: Page 1, 'sec- 0nd column, line 60, for"1-(aliaha-furfyl-Z-niti ethylene read -1-(a1phafi1ry1i-2-nitroethylene"; page 3, first column, line 58, below theformula,

insert --and. a carrier therefor";

pond" reed compound--;

and second column, line 5h, for "comline 58, for "aralyl" a --era1ky1--;

and that the said Letters Patent should he read with this correctiontherein that the same may conform to the record of the case in thePatent Officeo Sigied and sealed this 1st day of February, A. D. 19th.

(seal) Henry Van Arsdal'e Acting Commissioner oi Patents CERTIFICATE OFCORRECTION.

Patent No; 2,555,5auQ November 0, 1915.

EUCLID W. BOUSQUET, ET AL.

It is hereby certified that error appears in the printed specificationoi the above numbered patent requiring correction as follows: Page 1,beeand column, line 60, for "1-(aliaha-furiyl-Z-nitroethylene" read--1-(a1pha- -furyl\-2-nitroethy1ene; page 5, first column, line 58,below the formula,

insert --and a carrier therefor--; and second column, line 51;, for"compond read --compound--; line 58, for "aralyl" read y and that.

the said Letters Patent should be read with this correction therein thatthe same may confom to the record of the case in the Patent Office.

Signed and sealed this let day of February, A. D. 191 1;.

Henry Van Arsdal'e, (Seal) Acting Commissioner of Patents;

